【摘要】 采用二阶微扰理论的MP2/6-31G(d,p)方法对气相中烯丙基负离子与N2O的反应机理进行了理论计算研究,并在相同基组下进一步用CCSD(T)方法进行了单点能的校正.计算结果表明,该反应存在三条反应通道,产物分别为cis-CH2CHCNN-+H2O,trans-CH2CHCNN-+H2O和CH2CCH-+N2+H2O,其中生成cis-CH2CHCNN-和trans-CH2CHCNN-的两条通道为相互竞争的主反应通道,计算结果与实验相吻合.同时利用传统的过渡态理论,计算了各反应通道在298K时,速控步骤的反应速率常数k(T).更多还原

【Abstract】 s: The gas-phase reaction mechanism of allyl anion with N2O was investigated at the MP2/6-31G(d,p) level of the MP2 theory. The single-point energies have also been refined at the CCSD(T)/6-31G(d,p) level to get more accurate energies using the MP2/6-31G(d,p) optimized geometries. The computational results indicated that the reaction involved three reaction pathways to produce cis-vinyl-diazomethyl anion, trans-vinyl-diazomethyl anion, and allenyl anion. The major competition channels of the reaction which produced cis-vinyl-diazomethyl anion, and trans-vinyl-diazomethyl anion all involved two steps of α-H migration. Furthermore, all these rate-determing steps are the second α-H migration and the barriers are 89.79 and 97.93 kJ·mol-1, respectively. Distinctly, allenyl anion was formed through one α-H and one β-H migration and its rate-determing step was the rotation of the N10-O11 and N9-C3 bonds around N-N bond. The rate coefficients of the rate-determining step of all the reaction channels have also been calculated using statistic thermodynamics and conventional transition state theory at 298 K.更多还原